CN109569527A - A kind of multifunctional ceiling enclosure material based on cellulose base and preparation method thereof and its application - Google Patents
A kind of multifunctional ceiling enclosure material based on cellulose base and preparation method thereof and its application Download PDFInfo
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- CN109569527A CN109569527A CN201811532518.4A CN201811532518A CN109569527A CN 109569527 A CN109569527 A CN 109569527A CN 201811532518 A CN201811532518 A CN 201811532518A CN 109569527 A CN109569527 A CN 109569527A
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- 239000000463 material Substances 0.000 title claims abstract description 48
- 229920002678 cellulose Polymers 0.000 title claims abstract description 39
- 239000001913 cellulose Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 58
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims abstract description 38
- 230000003647 oxidation Effects 0.000 claims abstract description 38
- 238000010521 absorption reaction Methods 0.000 claims abstract description 31
- -1 aldehyde radical Chemical class 0.000 claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920000742 Cotton Polymers 0.000 claims abstract description 18
- 125000000524 functional group Chemical group 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000000975 dye Substances 0.000 claims abstract description 12
- 235000019441 ethanol Nutrition 0.000 claims abstract description 12
- 150000002500 ions Chemical class 0.000 claims abstract description 12
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 11
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 10
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims abstract description 7
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical group NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 6
- JGIDSJGZGFYYNX-YUAHOQAQSA-N indian yellow Chemical compound O1[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1OC1=CC=C(OC=2C(=C(O)C=CC=2)C2=O)C2=C1 JGIDSJGZGFYYNX-YUAHOQAQSA-N 0.000 claims abstract description 5
- 125000003368 amide group Chemical group 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 8
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 6
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 6
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 241001062009 Indigofera Species 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 claims description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 229940000489 arsenate Drugs 0.000 claims description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 2
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 239000004753 textile Substances 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims 1
- 229910052753 mercury Inorganic materials 0.000 claims 1
- 239000004744 fabric Substances 0.000 abstract description 29
- 241000872931 Myoporum sandwicense Species 0.000 abstract description 4
- 235000019991 rice wine Nutrition 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 230000001476 alcoholic effect Effects 0.000 abstract description 2
- 239000000356 contaminant Substances 0.000 abstract description 2
- 229940077449 dichromate ion Drugs 0.000 abstract description 2
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002585 base Substances 0.000 description 11
- 238000001179 sorption measurement Methods 0.000 description 8
- 241000209094 Oryza Species 0.000 description 5
- 235000007164 Oryza sativa Nutrition 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 235000009566 rice Nutrition 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000007306 functionalization reaction Methods 0.000 description 3
- 239000010903 husk Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 102000008946 Fibrinogen Human genes 0.000 description 1
- 108010049003 Fibrinogen Proteins 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- XOJVVFBFDXDTEG-UHFFFAOYSA-N Norphytane Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229940012952 fibrinogen Drugs 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- RECVMTHOQWMYFX-UHFFFAOYSA-N oxygen(1+) dihydride Chemical compound [OH2+] RECVMTHOQWMYFX-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention relates to multifunctional ceiling enclosure materials of a kind of cellulose base and its preparation method and application to sequentially pass through TEMPO oxidation/NaIO for cellulosic-based materials such as cotton, gauze, linen4Oxidation or NaIO4Oxidation/TEMPO oxidation process obtains the multi-functional absorption cloth with sub-micron and nanostructure using further surface graft modification.The absorption cloth contains special functional group's carboxyl, aldehyde radical, hydroxyl, amido, sulfydryl, sulfonic group, cyano, amide groups etc., can be used for adsorbing the ethyl alcohol in heavy metal ion (such as lead ion, dichromate ion), dyestuff (such as methylene blue, Indian yellow) and the absorption yellow rice wine in contaminant water to reduce alcoholic strength various aspects.
Description
Technical field
The present invention relates to the preparation technical fields of cellulose multifunctional material, and in particular to a kind of based on cellulose base
Multi-functional absorption cloth and preparation method thereof and its application, by pristine fibre element base fabric be used as raw material, sequentially pass through TEMPO aoxidize/
NaIO4Oxidation or NaIO4The multi-functional absorption containing carboxyl, aldehyde radical, hydroxyl that oxidation/TEMPO oxidation process is prepared
Cloth；Based on this, further other by the method introducing amino of surface grafting, sulfydryl, sulfonic group, cyano, amide groups etc.
Functional group, multifunctional ceiling enclosure material of the preparation for heavy metal ion and small organic molecule etc..
Background technique
Cellulosic-based material is widely used in the various aspects of mankind's food, clothing, housing and transportation, for example it includes cotton, flax that clothing, which is,
The textile materials such as cloth also include some non-woven fabric materials.In recent years, functionalization is carried out as platform using cellulosic-based material to repair
Decorations obtain various new function materials, and are applied to the various aspects such as separation, catalysis.Wherein, nano-cellulose is namely based on fibre
Plain based raw material is tieed up to prepare the typical case of nano material.The preparation method of nano-cellulose mainly includes TEMPO oxidation and sulphur
Sour water solution, the diameter of prepared nano-cellulose are about 5-20 nanometers, and length is 200 nanometers to several microns.Based on different
Preparation method, the functional group on nano-cellulose surface are respectively carboxyl, aldehyde radical, hydroxyl etc., and therefore, which is used extensively
In every field such as material, biomedicine, sensing, filterings.
As Chinese patent application CN 201510680385 disclose a kind of rice husk cellulose adsorbent and preparation method thereof and
Using.The technical solution adopted is that: rice husk is taken, after being washed with deionized, is put into thermostatic drying chamber, it is dry at 40-60 DEG C,
Taking-up is crushed in powdered, is taken powdered rice hulls to be slowly added to the concentrated sulfuric acid and is handled it, and heating water bath processing will be acidified
Stalk powder afterwards is washed with sodium bicarbonate, is washed with deionized water to neutrality, filtering, 40-70 DEG C of freeze-day with constant temperature is ground to partial size
It is 100-150 μm.The present invention is made functionalization adsorbent, gallium is adsorbed from the solution containing gallium by sulfuric acid modified rice husk, realizes
It is at low cost, turn waste into wealth, the advantages that large amount of adsorption.
Separately have Chinese patent application CN 201210455059 disclose a kind of bombax cotton adsorbent and preparation method thereof with
Using.This method comprises the following steps: (1) bombax cotton being placed in organic solvent and impregnated, then dry to obtain hydrophilic
The bombax cotton of processing；(2) bombax cotton of the hydrophilic treated is placed in progress basification in alkaline aqueous solution and obtains alkali
Change bombax cotton；(3) the alkalization bombax cotton is reacted with chelating agent obtains the bombax cotton adsorbent.The present invention
Selecting the bombax cotton with natural thin-walled hollow structure is raw material, and large specific surface area, modified effect is good, with prior art phase
Than adsorption rate is fast (can reach adsorption equilibrium in 2 minutes to lead ion cadmium ion), the adsorption capacity height (suction to lead ion
Attached amount maximum can achieve 311mg/g, can achieve 164mg/g to the adsorbance maximum of cadmium ion), facilitate De contamination, then inhale
Attached amount is high, is particularly suitable for the higher sewage treatment of initial concentration.
However, since the nano-cellulose of preparation is scattered in water with nanofiber or nanocrystalline form or other polarity are molten
In agent, it is therefore necessary to other machinery backing material is compound to actually use；Simultaneously as the decentralized medium of nano-cellulose
Mainly water, it is compound extremely difficult with hydrophobic material.So it is possible to solution be exactly keep cellulosic-based material
While prototype structure and property, the micro-nano structure of its inside is modified, obtain the mechanical performance not only with macroscopic view but also is had
There is the new material of microcosmic upper functionalization property.
Summary of the invention
In order to solve the above-mentioned problems in the prior art, the present invention provides a kind of multi-functional absorption of cellulose base
Material and preparation method thereof and its application, by cellulosic-based materials such as cotton, gauze, linen, sequentially pass through TEMPO oxidation/
NaIO4Oxidation or NaIO4Oxidation/TEMPO oxidation process obtains with sub-micron and receives using further surface grafting
The multi-functional absorption cloth of rice structure.The absorption cloth can be used for adsorbing heavy metal ion (such as lead ion, dichromate ion in contaminant water
Ion), dyestuff (such as methylene blue, Indian yellow) and absorption yellow rice wine in ethyl alcohol to reduce the various aspects such as alcoholic strength.
To achieve the above object, the invention adopts the following technical scheme:
A kind of multifunctional ceiling enclosure material of cellulose base, including be combined by one or more cellulosic-based materials, wherein extremely
A kind of rare cellulosic-based material is to sequentially pass through TEMPO oxidation/NaIO4Oxidation or NaIO4Oxidation/TEMPO oxidation, then into
The multi-functional functional group of the surface grafting of one step obtains the multifunctional ceiling enclosure material.
In some examples, the cellulosic-based material includes but is not limited to the weaving material such as cotton, gauze, linen
Expect, also the non-woven materials such as including filter paper, or combinations thereof.
In some examples, the functional group of the multifunctional ceiling enclosure material surface grafting includes carboxyl, aldehyde radical, hydroxyl, ammonia
Two or more functional groups such as base, sulfydryl, sulfonic group, cyano, amide groups or combinations thereof.
In some examples, the carboxyl and aldehyde radical are to sequentially pass through TEMPO oxidation/NaIO4Oxidation or NaIO4Oxidation/
What TEMPO oxidation process introduced；The functional group densities of the carboxyl are 0.1-3.0 mmol/g；The functional group of the aldehyde radical
Density is 0.1-12.0 mmol/g.
In some examples, the amino, sulfydryl, sulfonic group, cyano, amide groups etc. are drawn by the method for surface grafting
Enter；The various functional group densities such as amino, sulfydryl, sulfonic group, cyano, the amide groups are 0.1-10.0 mmol/g.
The present invention also protects the preparation method of the multifunctional ceiling enclosure material, and at least one cellulosic-based material is sequentially led to
Cross TEMPO oxidation/NaIO4Oxidation or NaIO4Oxidation/TEMPO oxidation process is prepared.
In some examples, the TEMPO is oxidized in the water for being placed in cellulosic substrates and having dissolved TEMPO and NaBr,
The NaClO solution of predetermined amount is added and keeps the pH value of system 11 or so, ethyl alcohol termination is added instead after reacting the regular hour
It answers, filters, deionized water is washed till neutrality, dry.
In some examples, the NaIO4It is oxidized to that place the product in a certain amount of NaIO4Aqueous solution in, room temperature or add
Thermal response 12 to 48 hours, product was filtered, washed, dries.
The present invention also protects the suction of heavy metal ion, dyestuff of the multifunctional ceiling enclosure material in absorption polluted source
Be accompanied by and the absorption of small organic molecule in application.
In some examples, the heavy metal ion include but is not limited to lead ion, mercury ion, cadmium ion, copper ion,
The anion such as the cation such as iron ion and chromate, MnO4, arsenate；The dyestuff includes but is not limited to methylene
The dyes of positive ion such as indigo plant, crystal violet, Nie's ear indigo plant and the anionic dyes such as Indian yellow, Congo red；The small organic molecule includes
Polarity and nonpolar organic compound, especially ethyl alcohol.
The present invention is aoxidized using TEMPO and NaIO4Oxidation process combines, can be by fibers such as cotton, gauze, linen
In plain sill, the methylol of the position C6 of cellulose is oxidized to carboxyl, while C2 and C3 hydroxyl is oxidized to aldehyde radical, obtains
There is multi-functional cellulosic-based material simultaneously；In addition, the original mechanicalness of material can be kept by control degree of oxidation
Can, adsorbing domain is directly applied to after oxidation.Since oxidation reaction is occurred in submicrometer structure level, degree of oxidation
It is suitable with traditional nano-cellulose.The present invention passes through further surface grafting amino, sulfydryl, sulfonic group, cyano, amide
Base obtains a series of cellulose base adsorbent materials, and can be used for the heavy metal ion in polluted source (such as lead ion, dichromic acid
Radical ion), the absorption of dyestuff (such as methylene blue, Indian yellow) and the absorption of the small organic molecule (alcohol as reduced yellow rice wine
Degree) etc..
Compared with prior art, the beneficial effects of the present invention are:
(1) it takes the lead in preparing cellulose multifunctional absorption cloth, and carrys out Effective Regulation by adjusting the order of two kinds of oxidation process and inhale
The functional group densities on attached cloth surface；More functional groups are introduced by surface grafting, more can simply prepare multifunctional ceiling
Enclosure material；
(2) cellulose multifunctional absorption cloth itself has good mechanical strength, and can keep this strong after surface-functionalized
Degree, can satisfy the needs of absorption completely；
(3) obtained by cellulose base absorption cloth have excellent mechanical performance and adsorption capacity, can be directly used for metal from
The various aspects such as the purifications of the polluted sources such as son, dyeing waste water and the absorption of small organic molecule.
Detailed description of the invention
It is further described with reference to the accompanying drawing:
Fig. 1 is the SEM figure that cellulose multifunctional adsorbs cloth.(a) NaIO4Aoxidize cloth；(b) TEMPO aoxidizes cloth；(c) TEMPO/
NaIO4Aoxidize cloth；(d) NaIO4/ TEMPO aoxidizes cloth；
Fig. 2 is the infrared spectrogram of (a) cotton of TEMPO oxidation front and back and the different oxidizabilities of (b) gauze；
Fig. 3 is the oxidizability of cotton and gauze with the variation of NaClO dosage；
Fig. 4 is NaIO4Aoxidize the infrared spectrogram of the cotton of front and back；
Fig. 5 is cotton through TEMPO and NaIO4Aoxidize the XRD spectra of front and back；
Fig. 6 is application of the cellulose multifunctional cloth on absorption (a) ethyl alcohol, (b) methylene blue, (c) lead ion；
Fig. 7 is the recycling efficiency of cellulose multifunctional cloth.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, to this
Invention is further elaborated.It should be appreciated that described herein, specific examples are only used to explain the present invention, without structure
At limitation of the present invention.
Example one: the preparation of cellulose multifunctional absorption cloth: a certain amount of gauze (or cotton), which is placed in, has dissolved in right amount
In the water of TEMPO and NaBr, the NaClO solution of predetermined amount is added and keeps the pH value of system 11 or so.When reacting certain
Between after ethyl alcohol be added terminate reaction, filtering, deionized water is washed till neutrality, dry.Place the product in a certain amount of NaIO4It is water-soluble
In liquid, room temperature or heating are reacted 12 to 48 hours.Product is filtered, washed, dries, and obtains the cellulose of TEMPO/NaIO4 oxidation
Quito function adsorbs cloth.
Example two: in turn by the oxidation process in example one, i.e., NaIO is first carried out4Oxidation, then carries out of short duration
TEMPO oxidation process, obtains NaIO4The cellulose multifunctional of/TEMPO oxidation adsorbs cloth, and the two has different surface carboxylics
The content of base and aldehyde radical.
Example three: TEMPO, NaIO will be passed through4The cloth of oxidation is observed with SEM, it is seen that fiber shape as shown in Figure 1
Looks.As can be seen that cotton or gauze can keep original pattern to be basically unchanged, that is, maintain by regulation degree of oxidation
Original mechanical strength, only introduces the functional groups such as carboxyl and aldehyde radical on surface.It can further be seen from figure 1 that elder generation NaIO4
Oxidation again TEMPO aoxidize obtained cellulose absorption cloth modification of surface morphology it is larger, it is meant that higher surface functionalization
Degree.
Example four: the cotton of different oxidizabilities and the infrared spectrogram of gauze are as shown in Figure 2.It will be clear that with
The raising of degree of oxidation, be located at 1604 cm-1The shock absorption peak of carboxylate radical also correspondingly enhance.Also, the oxidation of gauze
Degree is higher than cotton.It also can be seen that from the oxidizability in Fig. 3 with the variation of NaClO dosage, with the dosage of oxidant NaClO
Increase, the content of carboxylate radical first increases, then tends to be steady.This shows that oxidable C6 of the methylol of fiber surface gradually subtracts
It is few, finally tend to balance；And the oxidizability of gauze is higher with respect to cotton, and final oxidizability is up to 0.7-0.8 mMs every gram.
Equally, the NaIO in Fig. 44The content of aldehyde radical after oxidation also correspondingly increases, and range is about between 6-12 mMs every gram.
Example five: fibrinogen silk barathea cloth, NaIO4It is as shown in Figure 5 with the XRD spectrum of the cellulose cotton after TEMPO oxidation.
As can be seen that cotton fiber does not change the crystallization shape of cellulose after TEMPO is aoxidized, however pass through NaIO4After oxidation, though
Crystal form is had not been changed, crystallinity really decreases.So NaIO4Oxidation can change the crystallinity of cellulose, pass through TEMPO
After oxidation, the pattern of cellulose cotton has biggish change.
Example six: above cellulose multifunctional absorption cloth is respectively used to the absorption of ethyl alcohol in yellow rice wine to reduce alcohol
The absorption of lead ion in degree, the absorption of dyeing waste water Methylene Blue and heavy metal pollution water source, as a result as shown in Figure 6.It can
To find out either to small organic molecule ethyl alcohol, or to dye of positive ion methylene blue, and for heavy metal cation Pb2 +, cellulose multifunctional cloth all has good adsorption effect, such as can achieve 81.3 mg/ for the adsorption efficiency of lead ion
g.It is desorbed as shown in fig. 7, adsorbing cloth to the cellulose base for having adsorbed lead ion by using the hydrochloric acid of 1 mol/L, not only
Lead ion can be recycled, and it can be used repeatedly 5 times or more for the absorption cloth, still keeps 75% or more adsorption effect.
Following embodiment will be helpful to those skilled in the art and further understand the present invention, but not limit in any form
The present invention.It should be pointed out that those skilled in the art, without departing from the inventive concept of the premise, also
Several modifications and improvements can be made.These are all within the scope of protection of the present invention.
Claims (10)
1. a kind of multifunctional ceiling enclosure material of cellulose base, which is characterized in that including being answered by one or more cellulosic-based materials
It closes, wherein at least one cellulosic-based material is to sequentially pass through TEMPO oxidation/NaIO4Oxidation or NaIO4Oxidation/
TEMPO oxidation, further the multi-functional functional group of surface grafting obtains the multifunctional ceiling enclosure material.
2. the multifunctional ceiling enclosure material of cellulose base according to claim 1, which is characterized in that the cellulosic substrates
Material includes but is not limited to the textile materials such as cotton, gauze, linen, also the non-woven materials such as including filter paper, or combinations thereof.
3. the multifunctional ceiling enclosure material of cellulose base according to claim 1, which is characterized in that the multi-functional absorption
The functional group of material surface grafting includes that carboxyl, aldehyde radical, hydroxyl, amino, sulfydryl, sulfonic group, cyano, amide groups etc. are two or more
Functional group or combinations thereof.
4. the multifunctional ceiling enclosure material of cellulose base according to claim 3, which is characterized in that the carboxyl and aldehyde radical
It is to sequentially pass through TEMPO oxidation/NaIO4Oxidation or NaIO4What oxidation/TEMPO oxidation process introduced；The official of the carboxyl
It is 0.1-3.0 mmol/g that density, which can be rolled into a ball,；The functional group densities of the aldehyde radical are 0.1-12.0 mmol/g.
5. the multifunctional ceiling enclosure material of cellulose base according to claim 3, which is characterized in that the amino, sulfydryl,
Sulfonic group, cyano, amide groups etc. are introduced by the method for surface grafting；The amino, sulfydryl, sulfonic group, cyano, acyl
The various functional group densities such as amido are 0.1-10.0 mmol/g.
6. the preparation method of multifunctional ceiling enclosure material of any of claims 1-5, which is characterized in that will be at least one
Cellulosic-based material sequentially passes through TEMPO oxidation/NaIO4Oxidation or NaIO4Oxidation/TEMPO oxidation process is prepared.
7. preparation method according to claim 6, which is characterized in that the TEMPO, which is oxidized to, sets cellulosic substrates
In the water for having dissolved TEMPO and NaBr, the NaClO solution of predetermined amount is added and keeps the pH value of system 11 or so, reacts
Ethyl alcohol is added after regular hour and terminates reaction, filtering, deionized water is washed till neutrality, dry.
8. preparation method according to claim 6, which is characterized in that the NaIO4It is oxidized to that place the product in a certain amount of
NaIO4Aqueous solution in, room temperature or heating reaction 12 to 48 hours, product is filtered, washed, dries.
9. heavy metal ion, dye of the multifunctional ceiling enclosure material of any of claims 1-6 in absorption polluted source
Application in the absorption of material and the absorption of small organic molecule.
10. application as claimed in claim 9, which is characterized in that the heavy metal ion includes but is not limited to lead ion, mercury
The anion such as the cation such as ion, cadmium ion, copper ion, iron ion and chromate, MnO4, arsenate；The dyestuff
The including but not limited to dyes of positive ion such as methylene blue, crystal violet, Nie's ear indigo plant and the anionic dyes such as Indian yellow, Congo red；
The small organic molecule includes polarity and nonpolar organic compound, especially ethyl alcohol.
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| CN113522249A (en) * | 2021-06-29 | 2021-10-22 | 哈尔滨工程大学 | Antifouling hemp fiber material, preparation method and application thereof |
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| CN115156278A (en) * | 2022-06-23 | 2022-10-11 | 华南农业大学 | Application of nano oxidized cellulose in heavy metal contaminated soil remediation |
| CN115467156A (en) * | 2022-09-28 | 2022-12-13 | 郑州大学 | Test tube brush-shaped plant fiber and preparation method and application thereof |
| CN115820030A (en) * | 2022-12-27 | 2023-03-21 | 东莞市四辉表面处理科技有限公司 | Efficient paint remover and preparation method thereof |
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